Process and apparatus for reactivating catalyzers



' July 21, 19-25. 1,546,381

J. P. HARRIS PROCESS AND APPARATUS FOR REACTIVATING CATALYZERS Filed Dec :4, 1920 rlii "that in the course oi t v w; las ing:

"whom, it may concern:

it i IAOWH that 1,, JOHN P. liARRIS, a on of the United States, and a resident ilie city of Chicago, in the county of Cook and State of lilinois, have invented ew and useful improvements in a Process and r'kppariitns for Reactivating l' -i'yzers' and do hcrchy declare that the 22 full, clear, and exact descrip- .n-e some, reference being had to the o i'purvirnz druwingzs. and to the numeroi reference marked thereon, which form in the hvdrog en ion of oil especially edible oil like cotionseed oil a cntnlyzin z gent is r :ossnry in order to make the drogcn combine with the oil to form a -lll'2ti(l ronigmninl. This catalyze-er nsnconsists, of some find divided metal, ally nickelnll'ulinn.,. ilzitinnn'i. copper, on or the like l\l mi however. is chiefly nsijl on account of hiring coin'merciall nrziilniile.

"When a nickel (vital vet is used, it found one this catalyst loses its activity. This up iezrr he due to the ioisoning action of certain chemical substances, such as sulphur, phosphorus, chiorimx zinc, and compounds of ii 1, 8211119., and more pnrticulzn'ly the formation of or hilt) acid con'ipounds of nickel. 3 s methods have linen proposed 'i'or rogeiiorniing the catalyst. 'iiins, the nickel has won dissolved in acid, and reprecipitnb l as 2:. hydroxide by ammonium hydroxide, mill liar-n dried on n carrier and reduced in iilil b' illii'l ol livilrogen art 3 hi h tematnri- (."ilili" if}. in the oiher (us cl cutzil vsl has been o .ized on its snrtim'e, and then this routine: of oxide has been reduced in! heating in an atmosphere of h lrogzen.

' iihen lizirdci'iing cotton seed oil, the life of u carefully prepared i-zitzilyxer is likely to li i' very long nnd in some raises an entirely new lot of cutzilyzer is not required for vweli's in the constant operation oi d harden- 1 plant. in these cases the cutnlyzer is kept in :1 state of high activity for con- 75513112113, G1 CHTCAGO, XLLINOIS,

i ASSIGNOB TO THE ALLBRIGI-IT-NELL GUM- ?AZTY, E CFIGAGO, ILLINOIS, A CORPORATION 01? ILLINOIS,

iEEATR-ATUS FOR BEACTIVATING CATALYZERS.

'the finely divided metal off from' the oil,

dissolve it in an acid such as nitric acid, precipitate with ammonium hydroxide, wnsh. and put it through at series of processes. and finally recover it in the form of an organic acid salt of the metal, nickel acetate and fox-male being the salts that are ('(lil'lfi'lOllly used;

These processes of recovering are very laborious and expensive, but are ordinarily practiced by all-hardeners of oil in preference lo lniyingz entirely "fresh quantities of the celnlyst which would be even more eX- pensive.

This invention relates to an in'iproved method of rcactivuting catalytic motels, wlicrelrv the cntulyzer, after having}; been spent in the production of a number of lmlches of hydrogenated oil, is renewed to such an extent that an appreciable nunilior oi additional hatches of oil may he run with the some catalytic agent after trezitniei'it.

A further object of this invention the deroni -msition oi the foreign elements which poison the cntzilyzor and the bringing oi? the cntulyzer to un active state after such poisonin,

Still another object of the invention is to provide for the use of. small. additional quantities 0'! fresh cutnlyzer which can he used with 21 lzn'geliutch of Oll and old coini or by any other method, may he made active ae aiu.

- Other and further objects of this invention will be apparent from the disclosures in the specification and drawings The apparatus of the invention (in a pro tori-ed form) is illustrated in the drawings and hereinafter more fully described ()n the drawings:

The figure represents an elevation, partly in section, of my apparatus used in the react' ation of catalysers "For use'in the hydrogenation of oil As shown on the drawing 2 The reference numeral 1 indicates a tank such as is commonly used for the hydrogenation of oil, having therein a steam coil 2, provided with an inlet 3 and an outlet l, thissleam coil. being adapted for the purpose of heating: the oil to the required temperature.

Journalled in the tank 1, upon its longitudinal axis, is a hollow shaft 5 having attached thereto a mixing vane 6,, i This hollow shaft 5 has the mixing vane 6 attached at its lower end and revolvably positioned inside the hollow shaft 5 is the smaller shaft 8, upon which the lower mixing vane 7 is fixed. At the top of the shaft 5' is attached aheveled gear 9, and at the top of the shaft 8 is fixed the beveled gear 10. These gears are adapted to be driven by the gear 11 on the shaft- 12 having mounted thereon the driving pulley 13 and a loose pulley 14. As will be seen, revolution of the shaft 12 results in the driving of the vanes 6 and Tin opposite directions, Whereby a thorough mixing of the material is ensured.

An intake pipe 1:") for hydrogen gas is provided at the bottom of the taulc, and this pipe terminates in a spider 1.6 provided with a number of perforations through which the hydrogen gas escapes into the oil. A purge or exhaust pipe 17 is provided for the esc-ape'o'f excess try-- drogen and any carbon monoxide or other gas evolved fromthe decomposition of the nickel salt or other catalyst used. The tank may be proyided With any suitable means for the introduction of oil together 'Wltl). the spent catalyzer, A pipe 18 leads from the bottom of the tank to a pump 19, which pump is provided with two pipes 20 and 21, leading; ii) the coil 22 and the filter press 23 respectively.

The coil 92 is situated in a heating chamber 24, which is heated by any suitable means which. can be easily regulated, such as a series of gas burners. as shown at 25.

From the top (it the coilfii extends the pipe 38 leading lalclc into the llanl: l at the top thereof, tluilahle valves 2? and 28 are provided in the pipes 20 and F31 in order to control the passage of the oil together with the catalyzes through either 1e coil 22 or to the filter press as de s red. flhe opera ion is as follows:

The batch of oil containing the catalyzer put into the tank 1 and lrept thoroughly m xed by means oi the oppositely revolting mixing vanes G and K. At the same time steam is supplied through the coil 2 at shout N U. in order to raise the ilLlLCll oil to the required temperature upon which hydrogenation begins and the ten ore-tum rises to approximately 260 (1 11 my suitable apparatus may he used in place of the tank 1.

In operation, the hydrogenation process is to be poisoned, a connection is made with i the coil 22 whereby the oil, together with hydrogen and the spent catalyzer, is continuously pumped by means of the pump 19 through the coil 22 and the oil in passing through said coil is heated to approximate ly 220 6., after which it is discharged back into the tank 1 through pipe 26 and, joining the main body of the oil, immediately assumes a lower temperature.

It has-been found that as a result of this short exposure of the oil to an increased temperature for a short length of time, the strength of the catalyzcr has been increased to quite an appreciable extent and poisons eliminated.

In actual practice, after a run of say 20 to 22 or 23 hatches of oil has been made loy means of the'origina-l catalyzer, an additional number of runs corresponding to about one-third of t-lifeorig'inal number can be made after rcactigatiou of the catalyzer in the manner set forth above, which has already proved to be of enormous value to oil hardeners.

In operation the oil is heated loy meansof coil 2 to shout 165 and, in the-case of it spent catalyaer, the temperature does not rise when the hydrogen; is admitted which would ordinarily result owing to the exothermic action when the ca'talyzer is ac tive Thereapon the mixture is pumped througl'i the coil 22 and heated to about 220 (K, uhii-h, on account of the circulalion. gradually raises tintenuicrature of the 'i; the ironic 1 as the operation is coniinued until the oil mains s 'ienipersiburo "of'shouc 'culetion is discoiniinued will proceed fin stinos always maintained in- -r ial'ily under the highto he most eiicciive with sl-us used iii non of the process is as ed, ihe hydrogenation of oniplishcd in the appare- Ion, or any other sucapparatus, several and fllcered through usual i'nsnnc-r until the e spent, whereupon a cunt of fresh ceialyzer the valve 27, leading inend ihe pump 19 put 'J'OZA the cnibire quanei with the spent amount of fresh i oh the coii 22 at;

his results in i ounc of cola ,ionni number oi -n be secured from ici'zivstion of the catsin n a small amount of ity of che catalytic agenc has Ji'scticed, but it resulted in have more runs or heiches oh- ,hy the use oi the imshe" this apparatus or a short space of an L{l(;l'i3l9litll or seven runs or of oil he obtained which greetiihe eliicicncygoi the method and used. REJ'PQRES that she poisoning of the (new uc probably to the presence of the ;c or slczirate of the inciul, or some- "she presence of a. soup which is hy the decomposition o'i the stearizilyscs of the catalyst after use Show conleins nichcl pzilmiliaie, slicerwhich are decomposed by inc l mpor' ry hose 01 my iniention in the prcsi-i'u-o of? the reducing gas, such as hydrogen, which also acts to remove any poisoning agents from combination With the nic cl.

'" ii do the additional 6 or 3 runs are obrd by this method, the process can somehe ropes uniil the catalyst becomes posoned and can then not be M manner, hut must he rch'y r'lissolving in ii and a subsend forms of fatty r ml or some other form which has cn for: to he ihe niosb con n'i nuiuorl i" using the rulalvst. c

l'lnwcve, ic will be seen that an addiapproximately 33%- of the tol'al yield upon i a single batch of catalytic agent, will prove to he of inestimable advantage to oil hardeners in View of the quite considerable expense involved in the renewal of a catalytic agent by means of dissolving in acid and subsequent reduction and also the saving accomplished in the amount of new mate-- rial.

, it is obvious that this apparatus can he used primarily for the hydrogenation of oils and that whenever the catalyzer shows signs of becoming spent or poisoned, the valve 27 in the pipe can be opened and the pump 19 started, thereby causing e circulation of the oil to be hardened and the spent catalyst through the heated coils 22, whereupon e rcactivhlzion of the catalyst takes place on account of ishe intense llPfLlling with hydrogen which decomposes-end removes the foreign elements which poison the cwlelyzer. Circulation of the oil through the heated coil is continued until a, test shows shirt, the oil is again amenable to catalytic action. The usual catalytic action then takes place and is continued until complete saturation. Thus it will be seen filial) this sysiem of cet-slyzer reactivation can be readily applied to any process or system of hydrogenation.

I am aware the t numerous deaails of construction of the apparatus and of ihe method used may be varied through a Wide range Without departing from the principles of my invention, and I. therefore do not purpose limiting the patent granted otherwise than necessitated by the prior art.

I claim as my invention:

1. In an. oil hydrogenation process, that method of reectivating the catalyst which includes introducing an additional amount of fresh catalyst into the tank of hydro gen, oil, and spent catalyst, which is mainmined at a, temperature of approximately 190 C. to 210 (3., and pumping the mixture through a coiled pipe connected to die tank, said coiled pipe being maintained at a higher temperature than the oil in the tank. r

2. In an oil hydrogenation process, that method of reactivating the catalyst, which includes introducing an additional. :imoum of fresh catalyst into the tank ofhydrogen, oil, and spent catalyst, which is lllfllllmined at a tcmpcral'iu'c of approximately 190 C. to 210 (3., and pumping the mixture in small portions through a coiled pipe connected to the tank and maintained at. a temperature of npl'iroxinuitely 220 (ll 3. An ap mralus for inactivating catulyzors, including ii. tank having an inlet pipe for reducing f ns and an. cxluuislpipe or outlet, mixing means in tho tunic, a coil of 4L wees-5e:

pipe connected at its upper end to the up- In testimony whereof I have hereunto per portion of the tank and at its lower subscribed my name-in the presence'of fiwe end to the lower portion of the tank, said subscribing witnesses.

coil of pipe being situated outside the tank, JQHN P. HARRYS. 5 and adapted for additional heating, and a /Vitl lesses':

pump for circulating material from the tank ALBERT J, FIHE,

flu-on 111 the coil. H. Wsscovr WALKER. 

